CN108285145A - Three-dimensional multi-level structure nano silicon carbide, preparation method and application thereof - Google Patents
Three-dimensional multi-level structure nano silicon carbide, preparation method and application thereof Download PDFInfo
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- CN108285145A CN108285145A CN201810389073.2A CN201810389073A CN108285145A CN 108285145 A CN108285145 A CN 108285145A CN 201810389073 A CN201810389073 A CN 201810389073A CN 108285145 A CN108285145 A CN 108285145A
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 85
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 57
- 238000006722 reduction reaction Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002070 nanowire Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 238000003860 storage Methods 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 239000007772 electrode material Substances 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 239000011812 mixed powder Substances 0.000 claims abstract description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000011863 silicon-based powder Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000000643 oven drying Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000012300 argon atmosphere Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 12
- 230000009467 reduction Effects 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000004964 aerogel Substances 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract description 2
- 239000003990 capacitor Substances 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 description 17
- 239000000017 hydrogel Substances 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 238000004873 anchoring Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a preparation method of three-dimensional multilevel structure nano silicon carbide, which comprises the following steps: (1) synthesizing a carbon source aqueous solution: ultrasonically crushing a carbon source into deionized water to obtain a carbon source aqueous solution; (2) carrying out hydrothermal reaction and freeze drying to obtain reduced carbon source aerogel; (3) c, carbothermic reduction reaction: carrying out carbothermic reduction reaction on carbon source aerogel and excessive silicon/silicon dioxide mixed powder to preliminarily prepare three-dimensional nano silicon carbide; (4) cleaning: and soaking the three-dimensional silicon carbide subjected to carbothermic reduction by using mixed acid of hydrofluoric acid and concentrated nitric acid, and cleaning by using deionized water to obtain the final three-dimensional nano silicon carbide multilevel structure. The prepared three-dimensional nano silicon carbide multilevel structure consists of silicon carbide nanosheets and nanowires, shows good crystallinity and high strength, is simple in preparation method, and has wide application prospects in the fields of preparation of photoelectric catalysts and carriers thereof, gas sensing, hydrogen storage, super capacitors, battery electrode materials and the like.
Description
Technical field
The invention belongs to technical field of nano material, it is specifically related to a kind of three-dimensional multistage structure nano silicon carbide, prepares
Method and its application.
Background technology
Ceramic nano material, such as silicon carbide (SiC) have excellent corrosion resistance and inoxidizability, can be used as harshness
Filtering material in environment and catalyst carrier.The nano SiC material reported at present is mainly with nano whisker, nano particle etc.
Form exists, and easily reunites during use, specific surface area is caused to reduce.
Structure three-dimensional multistage structure can effectively increase the specific surface area of SiC, inhibit the agglomeration during use.Institute
It is basic unit that meaning three-dimensional multistage structure, which is by one-dimensional, two-dimensional nanostructure, is assembled by certain way.Chen et al.
(Chen J,Liu W,Yang T,Li B,Su J,Hou X and Chou K,A facile synthesis of a
three-dimensional flexible 3C-SiC sponge and its wettability,Crystal Growth&
Design,2014.DOI:10.1021/cg500723y) utilize gangue and carbon black for silicon source and carbon source, pass through carbon thermal reduction legal system
For three-dimensional 3C-SiC sponge structures.Chabi et al. (Chabi S, Rocha V G, Garcia-Tun ó n E, Ferraro C,
Saiz E,Xia Y and Zhu Y,ACS Nano,2016.DOI:10.1021/acsnano.5b05533) with chemical vapor deposition
Area method prepares three-dimensional graphene foam, and carries out carbothermic reduction reaction with SiO powder, is prepared for three-dimensional S iC foaming structures.But it is existing
The preparation method for the related three-dimensional S iC structures having, device therefor is complicated, and microstructure is mostly single nanometer sheet/nano wire, from
Enabling capabilities are not strong.
Invention content
Therefore, the purpose of the present invention is in view of the shortcomings of the prior art, provide a kind of three-dimensional multistage structure nano silicon carbide
The application for the product and product that preparation method and this method obtain, it is three-dimensional which solves gained in the prior art
The low problem of the specific surface area of nano silicon carbide silicon structure.
In order to solve the above technical problems, the present invention provides a kind of preparation method of three-dimensional multistage structure nano silicon carbide,
Include the following steps：
A) carbon source aqueous solution is prepared：By carbon source Ultrasonic Pulverization in deionized water, carbon source aqueous solution is obtained；
B) hydro-thermal reaction prepares carbon source aeroge：So that the carbon source aqueous solution obtained by step a) is mixed with ascorbic acid and carries out water
Then thermal response is freeze-dried, carbon source aeroge is made；
C) carbothermic reduction reaction：Carbon source aeroge obtained by step b) is mixed with excessive Si powder or silicon/silicon dioxide
It closes powder and carries out carbothermic reduction reaction, tentatively obtained three-dimensional manometer silicon carbide；
D) it cleans：By the three-dimensional manometer silicon carbide obtained by step c) using mixing acid soak, it is used in combination deionized water to clean, obtains
To final three-dimensional multistage structure nano silicon carbide.
Further, the carbon source in above-mentioned steps a) is graphene or graphene oxide, and obtained carbon source aqueous solution is dense
Degree is 2mg/ml.
Further, the condition of hydro-thermal reaction is in above-mentioned steps b)：Addition is 1 with carbon source mass ratio:2-1:4 (preferably
1:3-1:4) after ascorbic acid powder, it is heated to predetermined temperature using water heating kettle, and keep the temperature 6~12h, preferably soaking time is
10-12h.There is preferable three-dimensional appearance by the carbon source aeroge that this reaction condition makes, effectively increase specific surface area and hole
Gap rate.
Further, above-mentioned water heating kettle is heated to ranging from 150-180 DEG C of predetermined temperature.The carbon made by this temperature
Source hydrogel has better self-supporting effect, convenient for preserving and taking.
Further, the condition of freeze-drying is in above-mentioned steps b)：Make the quick-frozen molding of substance using liquid nitrogen or uses ice
Case makes material freeze be molded, and between temperature is -80 DEG C to -2 DEG C, 40~200Pa of air pressure, the time is 24-72 hours, to remove water
Point.
Further, above-mentioned liquid nitrogen make the quick-frozen molding temperature of substance be -80~-20 DEG C, refrigerator make material freeze at
The temperature of type is -15~-2 DEG C.It can effectively freeze and remove whole moisture in hydrogel by this temperature, to ensure carbon heat also
The integrality of structure when original reaction.
Further, the condition of carbothermic reduction reaction is in above-mentioned steps c)：Take the opposite excessive Si powder of carbon source or matter
Amount is than being 1:1 silicon/silicon dioxide mixed-powder, is layered on corundum crucible bottom, and carbon source aeroge is placed on mixed-powder,
Under argon gas atmosphere, it is warming up to 1300-1700 DEG C, preferably 1400~1500 DEG C, keeps the temperature 0.5~10h, preferably 1-3h；Wherein argon gas
Throughput is 0.2-3L/min, and heating rate is 1-20 DEG C/min, preferably 5-10 DEG C/min；Then cooled to room temperature；More
Preferably, carbon thermal reduction heating parameter is：1000 DEG C are warming up to 10 DEG C/min of rate, then with 5 DEG C/min of rate liter
Temperature is to 1400~1500 DEG C.It is carried out by this condition, the distillation of silicon source can be more advantageous to, so that carbon source is fully reacted with silicon source, completely
Generate silicon carbide structure.
Further, mixed acid cleaning step is in above-mentioned steps d)：Carbon thermal reduction product is placed in mixed acid, is stood
5-48h, preferably 12-24h, after be washed with deionized, be finally placed in oven drying, preferably in an oven with 80 DEG C of dry 6h,
Wherein mixed acid is：With 1:1-1:The hydrofluoric acid and concentrated nitric acid of 5 volume ratios mixing.
The present invention also provides a kind of three-dimensional multistage structure nano silicon carbide, it is obtained using above-mentioned preparation method, be by
SiC nanometer sheets, the three-dimensional multistage SiC structures of nano wire assembling.
The three-dimensional multistage structure nano silicon carbide prepared the present invention also provides the method for the present invention in photoelectric and its
Application in carrier, gas sensing, hydrogen storage, ultracapacitor and battery electrode material.This kind of material, can because of its large specific surface area
Further a large amount of doping heterogeneous elements form catalyst structure；And high porosity is also beneficial to gas absorption, storage, and electrolysis
The transmission of matter effectively increases gas sensing, storage and electric property.
The technique effect of the present invention：
The present invention provides three-dimensional multistage structure nano carbonization silicon preparation method, and it is solidifying to prepare three-dimensional carbon source gas by hydro-thermal reaction
Glue and carbothermic method generate SiC, can obtain by the three-dimensional multistage SiC structures of SiC nanometer sheets, nano wire assembling.Carbon source gas
The nanometer sheet self assembled three-dimensional structure of gel itself, is converted into SiC nanometer sheets in carbothermic reduction process, at the same with generation
SiC nanowire combines, and forms a kind of three-dimensional multistage structure.Three-dimensional multistage structure nano silicon carbide preparation side provided by the invention
Method, technical process is simple, is easy to implement large-scale production.And the method for the present invention is by carrying out carbon source aeroge and silicon source power
Carbothermic reduction reaction, obtains three-dimensional multistage structure nano silicon carbide, and gained three-dimensional structure can be further by chemical method at this
Fiber surface grows metal (such as nickel, cobalt, platinum, palladium) or oxide (iron oxide, cobalt oxide, nickel oxide etc.).
Three-dimensional multistage structure nano silicon carbide provided by the invention preferably maintains carbon source aerogel structure, and has excellent
Anticorrosive and high temperature resistance；With certain intensity, larger specific surface area and active site, photoelectric is being prepared
And its fields such as carrier, gas sensing, hydrogen storage, ultracapacitor and battery electrode material have a wide range of applications.
Three-dimensional manometer silicon carbide provided by the invention has extensively in catalyst carrier and ultracapacitor, Photocatalyzed Hydrogen Production field
General reference foreground, and have application potential on a sensor.
Description of the drawings
Fig. 1 is the optical photograph of gained three-dimensional manometer SiC multilevel hierarchies in the preferred embodiment of the present invention 1；
Fig. 2 is the SEM figures of 1 gained three-dimensional manometer SiC multilevel hierarchies of the preferred embodiment of the present invention；
Fig. 3 is the full spectrograms of XRD of 1 gained three-dimensional manometer SiC multilevel hierarchies of the preferred embodiment of the present invention.
Specific implementation mode
In order to make those skilled in the art more fully understand the present invention, with reference to the accompanying drawings and detailed description to this hair
It is bright to be described in further detail.Here it is to be noted that it in the accompanying drawings, the imparting of identical reference numeral is substantially had
The component part of same or like structure and function, and will omit about their repeated description.
The attached drawing constituted part of this application is used to provide further understanding of the present invention, schematic reality of the invention
Example and its explanation are applied for explaining the present invention, is not constituted improper limitations of the present invention.
The preparation method of three-dimensional multistage structure nano silicon carbide
A kind of preparation method of three-dimensional multistage structure nano silicon carbide, includes the following steps：
(1) carbon source solution is prepared：Graphene oxide powder is soluble in water, and carbon source aqueous solution is made in Ultrasonic Pulverization, prepares
Obtain 2mg/ml carbon source aqueous solutions；
(2) carbon source hydrogel is prepared：Carbon source aqueous solution obtained by step (1) is mixed with ascorbic acid, heating carries out hydro-thermal
Carbon source hydrogel is obtained by the reaction；
(3) it is freeze-dried：Carbon source hydrogel obtained by step (2) is freeze-dried, obtain redox graphene gas
Gel；
(4) carbothermic reduction reaction：By through step (3) freeze-drying after carbon source aeroge be placed on bottom lay excess silicon or
In the corundum crucible of silicon/silicon dioxide powder, heating carries out carbothermic reduction reaction, and rear cooled to room temperature tentatively obtains three
Tie up multistage SiC structures；
(5) concentrated acid cleaning, washing：Step (3) products therefrom is placed in the mixed acid of the hydrofluoric acid and concentrated nitric acid and is impregnated,
After be washed with deionized, then be placed in oven drying, obtain three-dimensional multistage structure nano SiC.
Following embodiment and comparative example are according to the preparation method step of above-mentioned three-dimensional multistage structure nano silicon carbide
It carries out, difference lies in use reagent and condition different；Argon gas used in each embodiment and comparative example be purity >=
99.99% high-purity argon gas；Chemical reagent is obtained by routine business approach unless otherwise specified used in other.
Embodiment 1
(1) graphene oxide solution is prepared：60mg graphene oxide sheets are dissolved in 30ml deionized waters, are then surpassed
Sound disperses, and so that solution is uniformly mixed (supersonic frequency 40kHz, ultrasonic power 100W mix 3h), it is molten to obtain graphene oxide
Liquid；
(2) hydro-thermal reaction：240mg ascorbic acid white powders are added into graphene oxide solution, and solution is transferred to
In 50ml water heating kettles, 6h is kept the temperature under the conditions of 180 DEG C, forms redox graphene hydrogel；
(3) it is freeze-dried：Redox graphene hydrogel obtained by step (2) is placed in refrigerator, 4h is freezed in -15 DEG C
It is allowed to be molded；Then redox graphene hydrogel is transferred in freeze drier, freeze-drying temperature is set and is arrived as 0 DEG C
Between room temperature, 40~200Pa of air pressure, the time is 24-72 hours, obtains redox graphene aeroge；
(4) carbon thermal reduction：Redox graphene aeroge obtained by step (3) is placed in bottom and lays excess silicon：Dioxy
SiClx=1：It in the corundum crucible of 1 (mass ratio) powder, is placed in tube furnace, under argon gas atmosphere protection, with 10 DEG C/min
1400 DEG C are warming up to, cooled to room temperature after heat preservation 2 hours tentatively obtains three-dimensional multistage SiC structures；
(5) nitration mixture cleans：Carbon thermal reduction product obtained by step (4) is placed in hydrofluoric acid (40%)：Concentrated nitric acid (65%)=
1：3 (volume ratios) mix in concentrated acid, impregnate 12h, after being washed by deionized water, are placed in 80 DEG C of dry 6h in baking oven, obtain three
Tie up multistage SiC nanostructures.
By the optical photograph of gained three-dimensional manometer SiC multilevel hierarchies in Fig. 1 preferred embodiment of the present invention 1 it is found that embodiment 1
In obtained three-dimensional multistage SiC nanostructure macroscopic views there is preferable three-dimensional appearance；By 1 institute of Fig. 2 preferred embodiment of the present invention
The SEM figures of three-dimensional manometer SiC multilevel hierarchies are obtained it is found that obtained three-dimensional multistage SiC nanostructures are by SiC nanometer sheets and nanometer
Line forms, and high porosity contributes to the anchoring of the loadings such as subsequent metal particle；By 1 gained three of Fig. 3 preferred embodiment of the present invention
The full spectrograms of XRD of nano SiC multilevel hierarchy are tieed up it is found that three-dimensional multistage SiC nanostructure main components are 3C-SiC phases, it is three-dimensional
The crystallinity of multilevel hierarchy is very high.
Embodiment 2
(1) graphene oxide solution is prepared：60mg graphene oxide sheets are dissolved in 30ml deionized waters, are then surpassed
Sound disperses, and so that solution is uniformly mixed (supersonic frequency 40kHz, ultrasonic power 100W mix 3h), it is molten to obtain graphene oxide
Liquid；
(2) hydro-thermal reaction：240mg ascorbic acid white powders are added into graphene oxide solution, and solution is transferred to
In 50ml water heating kettles, 12h is kept the temperature under the conditions of 180 DEG C, forms redox graphene hydrogel；
(3) it is freeze-dried：Redox graphene hydrogel obtained by step (2) is placed in refrigerator, 4h is freezed in -15 DEG C
It is allowed to be molded；Then redox graphene hydrogel is transferred in freeze drier, freeze-drying temperature is set and is arrived as 0 DEG C
Between room temperature, 40~200Pa of air pressure, the time is 24-72 hours, obtains redox graphene aeroge；
(4) carbon thermal reduction：Redox graphene aeroge obtained by step (3) is placed in bottom and lays excess silicon：Dioxy
SiClx=1:It in the corundum crucible of 1 (mass ratio) powder, is placed in tube furnace, under argon gas atmosphere protection, with 10 DEG C/min
1000 DEG C are warming up to, then 1300 DEG C are warming up to 5 DEG C/min, cooled to room temperature after heat preservation 3 hours tentatively obtains three-dimensional
Multistage SiC structures；
(5) nitration mixture cleans：Carbon thermal reduction product obtained by step (4) is placed in hydrofluoric acid (40%)：Concentrated nitric acid (65%)=
1:3 (volume ratios) mix in concentrated acid, impregnate for 24 hours, after being washed by deionized water, are placed in 80 DEG C of dry 6h in baking oven, obtain three
Tie up multistage SiC nanostructures.
Three-dimensional multistage SiC nanostructure macroscopic views obtained by the present invention have preferable three-dimensional appearance；This kind of SiC nano junction
Structure is made of SiC nanometer sheets with nano wire, and high porosity contributes to the anchoring of the loadings such as subsequent metal particle；The three-dimensional multistage
SiC nanostructure main components are 3C-SiC phases, and crystallinity is very high.
Embodiment 3
(1) graphene oxide solution is prepared：60mg graphene oxide sheets are dissolved in 30ml deionized waters, are then surpassed
Sound disperses, and so that solution is uniformly mixed (supersonic frequency 40kHz, ultrasonic power 100W mix 3h), it is molten to obtain graphene oxide
Liquid；
(2) hydro-thermal reaction：240mg ascorbic acid white powders are added into graphene oxide solution, and solution is transferred to
In 50ml water heating kettles, 12h is kept the temperature under the conditions of 180 DEG C, forms redox graphene hydrogel；
(3) it is freeze-dried：Redox graphene hydrogel obtained by step (2) is placed in refrigerator, 4h is freezed in -15 DEG C
It is allowed to be molded；Then redox graphene hydrogel is transferred in freeze drier, freeze-drying temperature is set and is arrived as 0 DEG C
Between room temperature, 40~200Pa of air pressure, the time is 24-72 hours, obtains redox graphene aeroge；
(4) carbon thermal reduction：Redox graphene aeroge obtained by step (3) is placed in bottom and lays excess silicon：Dioxy
SiClx=1:It in the corundum crucible of 1 (mass ratio) powder, is placed in tube furnace, under argon gas atmosphere protection, with 10 DEG C/min
1000 DEG C are warming up to, then 1700 DEG C are warming up to 5 DEG C/min, cooled to room temperature after heat preservation 3 hours tentatively obtains three-dimensional
Multistage SiC structures；
(5) nitration mixture cleans：Carbon thermal reduction product obtained by step (4) is placed in hydrofluoric acid (40%)：Concentrated nitric acid (65%)=
1:3 (volume ratios) mix in concentrated acid, impregnate for 24 hours, after being washed by deionized water, are placed in 80 DEG C of dry 6h in baking oven, obtain three
Tie up multistage SiC nanostructures.
Three-dimensional multistage SiC nanostructure macroscopic views obtained by the present invention have preferable three-dimensional appearance；This kind of SiC nano junction
Structure is made of SiC nanometer sheets with nano wire, and high porosity contributes to the anchoring of the loadings such as subsequent metal particle；The three-dimensional multistage
SiC nanostructure main components are 3C-SiC phases, and crystallinity is very high.
Embodiment 4
With embodiment 1 difference lies in：Carbon source uses graphene.
Three-dimensional multistage SiC nanostructure macroscopic views obtained by the present invention have preferable three-dimensional appearance；This kind of SiC nano junction
Structure is made of SiC nanometer sheets with nano wire, and high porosity contributes to the anchoring of the loadings such as subsequent metal particle；The three-dimensional multistage
SiC nanostructures part is 3C-SiC phases, and has part graphene residual.
Embodiment 5
With embodiment 1 difference lies in：It makes in carbon source aeroge and does not add ascorbic acid.
Three-dimensional multistage SiC nanostructure macroscopic views obtained by the present invention have preferable three-dimensional appearance；This kind of SiC nano junction
Structure is made of SiC nanometer sheets with nano wire, and high porosity contributes to the anchoring of the loadings such as subsequent metal particle；The three-dimensional multistage
SiC nanostructure main components are 3C-SiC phases, and crystallinity is very high.
Comparative example 1
This comparative example preparation process is same as Example 1, differs only in：Silicon source used is pure Si powder in step (4)
End, gained three-dimensional multistage structure are only made of SiC nanometer sheets.
The three-dimensional multistage structure nano SiC that the method for the present invention is prepared adapts to harsh environment, for photoelectric and
In its carrier, gas sensing, hydrogen storage, ultracapacitor and battery electrode material, have in catalyst carrier, ultracapacitor field
Reference foreground extensively, and have application potential on a sensor.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.Therefore, protection scope of the present invention is answered
This is subject to the protection scope in claims.
Claims (10)
1. a kind of preparation method of three-dimensional multistage structure nano silicon carbide, which is characterized in that include the following steps：
A) carbon source aqueous solution is prepared：By carbon source Ultrasonic Pulverization in deionized water, carbon source aqueous solution is obtained；
B) carbon source aeroge is prepared：So that the carbon source aqueous solution obtained by step a) is mixed with ascorbic acid, carries out hydro-thermal reaction, then
Carbon source aeroge is made in freeze-drying；
C) carbothermic reduction reaction：By the mixing of carbon source aeroge and excessive Si powder or silicon and silica obtained by step b)
Powder carries out carbothermic reduction reaction, tentatively obtained three-dimensional manometer silicon carbide；
D) it cleans：By the three-dimensional manometer silicon carbide obtained by step c) using mixing acid soak, it is used in combination deionized water to clean, obtains most
Whole three-dimensional multistage structure nano silicon carbide.
2. the preparation method of three-dimensional multistage structure nano silicon carbide as described in claim 1, which is characterized in that the step a)
In carbon source be graphene or graphene oxide, and obtained carbon source concentration of aqueous solution be 2mg/ml.
3. the preparation method of three-dimensional multistage structure nano silicon carbide as described in claim 1, which is characterized in that the step b)
The condition of middle hydro-thermal reaction is：Addition is 1 with carbon source mass ratio:2-1:After 4 ascorbic acid powder, it is heated to using water heating kettle
Predetermined temperature, and keep the temperature 6~12h.
4. the preparation method of three-dimensional multistage structure nano silicon carbide as claimed in claim 3, which is characterized in that the water heating kettle
It is heated to ranging from 150-180 DEG C of predetermined temperature.
5. the preparation method of three-dimensional multistage structure nano silicon carbide as described in claim 1, which is characterized in that the step b)
The condition of middle freeze-drying is：Make the quick-frozen molding of substance using liquid nitrogen or so that material freeze is molded using refrigerator, temperature is -80 DEG C
To between -2 DEG C, 40~200Pa of air pressure, the time is 24-72 hours, to remove moisture.
6. the preparation method of three-dimensional multistage structure nano silicon carbide as claimed in claim 5, which is characterized in that the liquid nitrogen makes
The quick-frozen molding temperature of substance is -80~-20 DEG C, and refrigerator makes the molding temperature of material freeze be -15~-2 DEG C.
7. the preparation method of three-dimensional multistage structure nano silicon carbide as described in claim 1, which is characterized in that the step c)
The condition of middle carbothermic reduction reaction is：It is 1 to take the opposite excessive Si powder of carbon source amount or mass ratio:1 silicon：Silica mixes
Powder is closed, corundum crucible bottom is layered on, carbon source aeroge is placed on mixed-powder and is warming up to 1300- under an argon atmosphere
1700 DEG C, 0.5~10h is kept the temperature, wherein argon stream amount is 0.2-3L/min, and heating rate is 1-20 DEG C/min；Then natural
It is cooled to room temperature.
8. the preparation method of three-dimensional multistage structure nano silicon carbide as described in claim 1, which is characterized in that the step d)
Middle cleaning step is：Carbothermic reduction reaction product-three-dimensional manometer silicon carbide obtained by step c) is placed in mixed acid, 5- is stood
48h, after be washed with deionized, be finally placed in oven drying, wherein mixed acid is：With 1:1-1:The hydrogen fluorine of 5 volume ratios mixing
Acid and concentrated nitric acid.
9. a kind of three-dimensional multistage structure nano silicon carbide, which is characterized in that it is wanted using any right in such as claim 1~8
It asks the preparation method to obtain, is the three-dimensional multistage SiC structures assembled by SiC nanometer sheets, nano wire.
10. a kind of three-dimensional multistage structure nano silicon carbide as claimed in claim 9 is passed in photoelectric and its carrier, gas
Application in sense, hydrogen storage, ultracapacitor and battery electrode material.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485047A (en) * | 2018-12-14 | 2019-03-19 | 中国科学院深圳先进技术研究院 | Three-dimensional structure silicon carbide and its preparation method and application |
| CN109817474A (en) * | 2019-01-30 | 2019-05-28 | 宁波工程学院 | A kind of preparation method of chip level full solid state SiC supercapacitor |
| CN110668446A (en) * | 2019-10-31 | 2020-01-10 | 哈尔滨工业大学 | Preparation method of high-temperature-resistant SiC aerogel |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718217A (en) * | 2012-05-18 | 2012-10-10 | 湖北大学 | High purity linear silicon carbide powder and preparation method |
| CN103496703A (en) * | 2013-10-11 | 2014-01-08 | 西南科技大学 | Preparation method of fibrous nano silicon carbide |
| CN103834988A (en) * | 2014-03-24 | 2014-06-04 | 中国科学院山西煤炭化学研究所 | Preparation method of nano silicon carbide whisker |
| CN105600785A (en) * | 2015-12-24 | 2016-05-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method for silicon carbide aerogel |
| CN106832758A (en) * | 2017-03-06 | 2017-06-13 | 东北大学秦皇岛分校 | A kind of Graphene/phenolic resin heat-conductive composite material and preparation method thereof |
-
2018
- 2018-04-27 CN CN201810389073.2A patent/CN108285145A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718217A (en) * | 2012-05-18 | 2012-10-10 | 湖北大学 | High purity linear silicon carbide powder and preparation method |
| CN103496703A (en) * | 2013-10-11 | 2014-01-08 | 西南科技大学 | Preparation method of fibrous nano silicon carbide |
| CN103834988A (en) * | 2014-03-24 | 2014-06-04 | 中国科学院山西煤炭化学研究所 | Preparation method of nano silicon carbide whisker |
| CN105600785A (en) * | 2015-12-24 | 2016-05-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method for silicon carbide aerogel |
| CN106832758A (en) * | 2017-03-06 | 2017-06-13 | 东北大学秦皇岛分校 | A kind of Graphene/phenolic resin heat-conductive composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| LIAN SUN ET AL: ""A Novel Silicon Carbide Nanosheet for High‐Performance Humidity Sensor"", 《ADVANCED MATERIALS INTERFACES》 * |
| SAKINEH CHABI ET AL: ""Ultralight, Strong, Three-Dimensional SiC Structures"", 《ACS NANO》 * |
| 陆飞: ""混合型过渡金属氧化物和硫化物纳米材料的设计制备及其超级电容性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (15)
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